Cationically polymerizable resin composition

Abstract

A cationically polymerizable resin composition which comprises (A) a compound containing at least one ring selected from the group consisting of an oxirane ring and an oxetane ring; (B) an onium salt; (C) an organic peroxide; and (D) an alkaline filler except for a hydroxide.

What is claimed is:  
     
       1. A cationically polymerizable resin composition which comprises 
       (A) a compound containing at least one ring selected from the group consisting of an oxirane ring and an oxetane ring, said compound being selected from the group consisting of a bisphenol A epoxy resin having an average molecular weight of 400 or less, p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether, a bisphenol F epoxy resin., a phenol novolak epoxy resin having an average molecular weight of 570 or less, vinyl(3,4-cyclohexene)dioxide, (3,4-epoxycyclohexyl)methyl 3,4-epoxycyclohexylcarboxylate, bis(3,4epoxy-6-methylcyclohexylmethyl)adipate, 2-(3,4-epoxycyclohexyl)5,1-spiro(3,4-epoxycyclohexyl)-m-dioxane, diglycidyl hexahydrophthalate, diglycidyl 3-methylhexahydrophthalate, diglycidyl hexahydroterephthalate, diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylene diamine, tetraglycidyl-bis(aminomethyl)cyclohexane, 1,3-diglycidyl-5-methyl-5-ethylhydantoin, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, α-pinene oxide, allyl glycidyl ether, glycidyl methacrylate, 1-vinyl-3,4-epoxycyclohexane, (poly)ethyleneglycol diglycidyl ether, (poly)propyleneglycol diglycidyl ether, butanediol glycidyl ether, neopentylglycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl(methyl)dimethoxy silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy silane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxy silane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-hexyloxymethyloxetane, 3-ethyl-3-allyloxymethyloxetane, 3-ethyl-3-benzyloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-carboxyloxetane, bis-{[ethyl(3-oxetanyl)]methyl}ether, 1,4-bis[ethyl(3-oxetanyl)methoxymethyl]benzene, bis{[ethyl(3-oxetanyl)]methyl}carbonate, bis{[ethyl(3-oxetanyl)]ethyl}adipate, bis{[ethyl(3-oxetanyl)]methyl}terephthalate, bis{[ethyl(3-oxetanyl)]methyl}-1,4-cyclohexanecarboxylate, bis{4-[ethyl(3-oxetanyl)methoxycarbonylamino]phenyl}methane, α,ω-bis-{3-[1-ethyl(3-oxetanyl)methoxy]propyl(polydimethylsiloxane) and oligo(glycidyloxetane-co-phenylglycidyl ether);  
       (B) at least one onium salt in an amount of 2 to 8 parts by weight based on 100 parts by weight of (A), said onium salt being selected from the group consisting of an iodonium salt, a sulfonium salt, an ammonium salt, a phosphonium salt, a diazonium salt and a pyridinium salt of the following formula:                    
        wherein  
       R is the same or different and is a straight or branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, said cycloalkyl group being unsubstituted or substituted by an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a monovalent substituted hydrocarbon group selected from the group consisting of 4-hydroxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-cyanophenyl, 4-chlorophenyl, 4-acetoxyphenyl, 4-propanoylphenyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 4-methoxybenzyl, 4-ethoxybenzyl, 4-t-butoxybenzyl, 4-nitrobenzyl and 4-cyanobenzyl,  
       E 1  is an iodine atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a diazo group or an unsubstituted or ring-substituted pyridinio group,  
       E 2  is a sulfur atom or a nitrogen atom,  
       Z is a zwitter ion which is BF 4 , PF 4 , AsF 6 , SbF 6  or (C 6 H 5 ) 4 B,  
       a is 2 when E 1  is an iodine atom, a is 3 when E 1  is a sulfur atom, a is 4 when E 1  is a nitrogen atom or a phosphorus atom, or  
       a is 1 when E 1  is a diazo group or an unsubstituted or ring-substituted pyridinio group,  
       b is 1 when E 2  is a sulfur atom or b is 2 when E 2  is a nitrogen atom, and  
       c is 4 or 5;  
       (C) an organic peroxide in an amount of 0.01 to 1 part by weight based on 100 parts by weight of (A); and  
       (D) an alkaline filler except for a hydroxide, said alkaline filler being in an amount of 5 to 15 fold of the amount of (B).  
     
     
       2. The composition according to  claim 1 , wherein (A) is a liquid state at normal temperature. 
     
     
       3. The composition according to  claim 2 , wherein (A) exhibits fluidity at a temperature of 25 to 40° C. 
     
     
       4. The composition according to  claim 1 , wherein Component (B) is a salt of B(C 6 H 5 ) 4 . 
     
     
       5. The composition according to  claim 1 , wherein Component (C) is a dialkylperoxide, a peroxyketal or an alkylperoxy ester. 
     
     
       6. The composition according to  claim 1 , wherein Component (D) is a filler selected from the group consisting of calcium carbonate, magnesium oxide and zinc oxide. 
     
     
       7. The composition according to  claim 1 , wherein the composition further comprises Component (E) a neutral or alkaline colorant. 
     
     
       8. The composition according to  claim 1 , wherein (B) is the pyridinium salt. 
     
     
       9. The composition according to  claim 8 , wherein R is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, cyclohexyl, phenyl, 4-tolyl, 2,4-xylyl, 1-naphthyl, benzyl, 2-methylbenzyl, 4-methylbenzyl, 2-phenylethyl, 1-naphthylmethyl, vinyl, allyl and butenyl; and E is 2-methylpyridinio, 4-methylpyridinio, 2,4-dimethylpyridinio, 2-cyanopyridinio, 4-cyanopyridinio, 2-methoxycarbonylpyridinio, 4-methoxycarbonylpyridinio, 2-ethoxycarbonylpyridinio and 4-ethoxycarbonylpyridinio. 
     
     
       10. The composition according to  claim 1 , wherein (B) is at least one onium salt which is a hexafluoroantimonate salt or a tetrakis(pentafluorophenyl)boron, of diphenyl iodonium, phenyl(4-tolyl)iodonium, phenyl(4-cumyl)iodonium, phenyl(4-t-butylphenyl)iodonium, di(4-tolyl)iodonium, 4-tolyl(4-cumyl)iodonium, 4-tolyl(4-t-butylphenyl)iodonium, di(4-cumyl)iodonium, 4-cumyl(4-t-butylphenyl)iodonium, di(4-t-butylphenyl)iodonium, phenyl(4-methoxyphenyl)iodonium, bis(4-methoxyphenyl)iodonium, phenylbenzyl iodonium, triphenyl sulfonium, diphenyl(4-t-butylphenyl)sulfonium, tritolyl sulfonium, tris(4-hydroxy-phenyl)sulfonium, tris(4methoxyphenyl)sulfonium, tris(4-ethoxyphenyl)sulfonium, tris(acetoxyphenyl)sulfonium, methyl(4-hydroxyphenyl)benzyl sulfonium or methyl(4-methoxyphenyl)-1-naphthylmethyl sulfonium. 
     
     
       11. The composition according to  claim 10 , wherein (C) is an organic peroxide selected from the group consisting of dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 1,1-bis-(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, ethyl 3,3-(t-butylperoxy)butyrate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxy-2-ethyl hexanoate, t-butylperoxy isobutyrate, t-butylperoxy maleate and t-butylperoxy benzoate. 
     
     
       12. The composition according to  claim 11 , wherein (D) is selected from the group consisting of calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide, titanium oxide and aluminum oxide. 
     
     
       13. The composition according to  claim 12 , which further comprises 0.1 to 10 parts by weight of (E) a neutral or alkaline colorant based on 100 parts by weight of (A). 
     
     
       14. The composition according to  claim 13 , wherein (E) is at least one colorant selected from the group consisting of carbon black, black lead oxide, a Cr—Cu complex oxide, a complex oxide of Cu—Fe—Mn, red iron oxide, cobalt blue, a chromophthal colorant, a quinacridone colorant and a phthalocyanine pigment. 
     
     
       15. The composition according to  claim 1 , wherein the alkaline filler is a filler in which an extract solution extracted with pure water results in a pH of. 7 to 10.